CN105008897A - Mercury monitor - Google Patents
Mercury monitor Download PDFInfo
- Publication number
- CN105008897A CN105008897A CN201480008675.9A CN201480008675A CN105008897A CN 105008897 A CN105008897 A CN 105008897A CN 201480008675 A CN201480008675 A CN 201480008675A CN 105008897 A CN105008897 A CN 105008897A
- Authority
- CN
- China
- Prior art keywords
- gas
- mercury
- window
- analyzing container
- ports
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 title claims abstract description 54
- 229910052753 mercury Inorganic materials 0.000 title claims abstract description 48
- 238000010521 absorption reaction Methods 0.000 claims abstract description 18
- 239000007789 gas Substances 0.000 claims description 120
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 41
- 239000000523 sample Substances 0.000 claims description 36
- 239000007788 liquid Substances 0.000 claims description 22
- 239000012530 fluid Substances 0.000 claims description 10
- 238000000926 separation method Methods 0.000 claims description 9
- 230000005855 radiation Effects 0.000 claims description 8
- 230000003287 optical effect Effects 0.000 claims description 5
- 239000012159 carrier gas Substances 0.000 claims description 2
- 238000004458 analytical method Methods 0.000 abstract description 8
- 239000012190 activator Substances 0.000 abstract 1
- 239000003570 air Substances 0.000 description 15
- 239000000443 aerosol Substances 0.000 description 13
- 150000003839 salts Chemical class 0.000 description 13
- 238000000034 method Methods 0.000 description 10
- 239000002245 particle Substances 0.000 description 9
- 230000008569 process Effects 0.000 description 7
- 239000003708 ampul Substances 0.000 description 6
- 238000005086 pumping Methods 0.000 description 6
- 239000010453 quartz Substances 0.000 description 6
- 238000010992 reflux Methods 0.000 description 6
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 6
- 238000010586 diagram Methods 0.000 description 5
- 238000001704 evaporation Methods 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- 230000002829 reductive effect Effects 0.000 description 5
- 238000005070 sampling Methods 0.000 description 5
- 230000035945 sensitivity Effects 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 230000008020 evaporation Effects 0.000 description 4
- 239000013505 freshwater Substances 0.000 description 4
- 238000005259 measurement Methods 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 3
- 150000001875 compounds Chemical class 0.000 description 3
- 230000007547 defect Effects 0.000 description 3
- 239000012153 distilled water Substances 0.000 description 3
- 238000001802 infusion Methods 0.000 description 3
- 238000012544 monitoring process Methods 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000000779 smoke Substances 0.000 description 3
- 239000003039 volatile agent Substances 0.000 description 3
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 238000009833 condensation Methods 0.000 description 2
- 230000005494 condensation Effects 0.000 description 2
- 238000010494 dissociation reaction Methods 0.000 description 2
- 230000005593 dissociations Effects 0.000 description 2
- 239000000428 dust Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- 229910052751 metal Inorganic materials 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 238000006213 oxygenation reaction Methods 0.000 description 2
- 238000002360 preparation method Methods 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- -1 salt compound Chemical class 0.000 description 2
- 239000010865 sewage Substances 0.000 description 2
- 238000004088 simulation Methods 0.000 description 2
- 239000012086 standard solution Substances 0.000 description 2
- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 1
- QAOWNCQODCNURD-UHFFFAOYSA-L Sulfate Chemical compound [O-]S([O-])(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-L 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- 239000012080 ambient air Substances 0.000 description 1
- 238000000429 assembly Methods 0.000 description 1
- 230000000712 assembly Effects 0.000 description 1
- 238000000889 atomisation Methods 0.000 description 1
- 230000004888 barrier function Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000007664 blowing Methods 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 230000008021 deposition Effects 0.000 description 1
- 230000006866 deterioration Effects 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000002045 lasting effect Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 229940100892 mercury compound Drugs 0.000 description 1
- 150000002731 mercury compounds Chemical class 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000004062 sedimentation Methods 0.000 description 1
- 239000007787 solid Substances 0.000 description 1
- 239000000243 solution Substances 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- 239000007921 spray Substances 0.000 description 1
- 238000005507 spraying Methods 0.000 description 1
- 239000000758 substrate Substances 0.000 description 1
Classifications
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/03—Cuvette constructions
- G01N21/0332—Cuvette constructions with temperature control
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01J—MEASUREMENT OF INTENSITY, VELOCITY, SPECTRAL CONTENT, POLARISATION, PHASE OR PULSE CHARACTERISTICS OF INFRARED, VISIBLE OR ULTRAVIOLET LIGHT; COLORIMETRY; RADIATION PYROMETRY
- G01J3/00—Spectrometry; Spectrophotometry; Monochromators; Measuring colours
- G01J3/28—Investigating the spectrum
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/11—Filling or emptying of cuvettes
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/01—Arrangements or apparatus for facilitating the optical investigation
- G01N21/15—Preventing contamination of the components of the optical system or obstruction of the light path
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/17—Systems in which incident light is modified in accordance with the properties of the material investigated
- G01N21/25—Colour; Spectral properties, i.e. comparison of effect of material on the light at two or more different wavelengths or wavelength bands
- G01N21/31—Investigating relative effect of material at wavelengths characteristic of specific elements or molecules, e.g. atomic absorption spectrometry
- G01N21/3103—Atomic absorption analysis
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/714—Sample nebulisers for flame burners or plasma burners
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N21/00—Investigating or analysing materials by the use of optical means, i.e. using sub-millimetre waves, infrared, visible or ultraviolet light
- G01N21/62—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light
- G01N21/71—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited
- G01N21/74—Systems in which the material investigated is excited whereby it emits light or causes a change in wavelength of the incident light thermally excited using flameless atomising, e.g. graphite furnaces
-
- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N33/00—Investigating or analysing materials by specific methods not covered by groups G01N1/00 - G01N31/00
- G01N33/0004—Gaseous mixtures, e.g. polluted air
- G01N33/0009—General constructional details of gas analysers, e.g. portable test equipment
- G01N33/0027—General constructional details of gas analysers, e.g. portable test equipment concerning the detector
- G01N33/0036—General constructional details of gas analysers, e.g. portable test equipment concerning the detector specially adapted to detect a particular component
- G01N33/0045—Hg
Landscapes
- Physics & Mathematics (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- General Physics & Mathematics (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Nuclear Medicine, Radiotherapy & Molecular Imaging (AREA)
- Plasma & Fusion (AREA)
- Combustion & Propulsion (AREA)
- Food Science & Technology (AREA)
- Medicinal Chemistry (AREA)
- Environmental & Geological Engineering (AREA)
- General Life Sciences & Earth Sciences (AREA)
- Geology (AREA)
- Investigating Or Analysing Materials By Optical Means (AREA)
- Optical Measuring Cells (AREA)
Abstract
A mercury monitor comprising a sample input unit, a thermal atomizer, an analysis vessel capable of being heated, a gas collector unit, and a drainage activator. The container is optionally connected to an atomic absorption spectrometer and comprises at least two output gas ports and at least one input gas port located in a central portion thereof. A drainage actuator is connected to the sample input unit so that a sample to be analyzed can be introduced into the thermal atomizer and apertures through which gas can be fed are provided on both sides of the body of the analysis vessel between an opening and an output gas port nearest to the opening.
Description
Claimed invention relates to the analytic system automatically measuring mercury concentration, and may be used for monitoring industry and sanitary sewage and burning gases.
At present it is known that mercury vapor analyzer PA-2 mercury industrial analysis instrument [1] of German Mercury instrument, it is designed to the mercury concentration in the industrial sewage of the enterprise, cogeneration plant, treatment facility etc. that continuous coverage is devoted to burn away the refuse.Mercury watch-dog comprises: sample preparation module, wherein utilizes the preliminary oxidation of corresponding reagent generation sample; Recovery module, wherein makes mercury be reduced to state of atom when adding reductive agent; Gas exchange units, wherein mercury element discharges from fluid sample and enters vector gas; And analyzing container, wherein vector gas conveying mercury element, and wherein limit the amount of the mercury discharged with atomic absorption method.
The defect of simulation is: need to perform previous work and select to make the method for sample oxidation (depending on sample substrate and mercury existence form in the sample to which); Requirement for height is in sample preparation and purity mercury being reduced to the middle reactant used of state of atom; And short-period watch-dog is unattended, this is origin self-reductivity solution and causing from the reductive agent of sample and the precipitation of kieserohalosylvite respectively.In addition, need to fill continually, until compensate the reactant exhausted.
Become known for the device [2] monitoring mercury emissions, it comprises: input block, and described input block is used for analytical gas sample; Thermospray, the generation of wherein all mercury compound dissociation mercury elements; Analyzing container, described analyzing container can be assigned to reduce the oxygenation efficiency of mercury element with suitable dissociation product and matrix group by heating; Atomic Absorption Spectrometer, described Atomic Absorption Spectrometer allows to measure mercury element and the impact significantly reducing matrix.
The defect of simulation is: short-period watch-dog is unattended, and this is caused by the pollution of analyzing container window; Cannot the device of usage monitoring process water, this is because the high concentration dissolving salt be included in process water is deposited on the wall of input sample unit and Thermospray, also cause barrier gas passage.
The mercury watch-dog [3] of burning gases MERCEM300Z mercury vapor analyzer of Sick company of Germany is immediate technology, its by sampling probe, gas line, sample input block, Thermospray, can be formed by analyzing container, Atomic Absorption Spectrometer and the sucking-off pump heated.Burning gases sampling probe absorbs and is transported to the importation of watch-dog.Other gas passes in Thermospray, and all mercury that the existence form wherein with it in burning gases has nothing to do are converted into element form; And enter analyzing container, wherein limit mercury concentration by Atomic Absorption Spectrometer.Manufacture sucking-off pump with the form of displacer and be attached to analyzing container outlet.The temperature of Thermospray and analyzing container is 1000 DEG C.
The defect of prototype is: short-period watch-dog is unattended, and this is caused by the pollution of analyzing container window.Burning gases have quite complicated Cheng Fen – and are released and are formed at fossil-fuel-fired various gas (CO
2, SO
2, NO, NOx, water vapour, HCl, HF etc.), and smoke particle.The interaction of corrosive gas and smoke particle and sampling system element causes the generation of volatile compound, because gas temperature is about 1000 DEG C, and the temperature of the window in outside is much lower, so volatile compound is deposited on the window of analyzing container.The pollution of window causes the intensity of the probe radiation significantly reducing Atomic Absorption Spectrometer, and result causes the deterioration of analysis characteristic, even causes and cannot measure.For the same reason, this prototype can not be used to limit the content of mercury in the process water (comprising the chloride of the metal of high percent concentration and the water of sulfate (kieserohalosylvite)) of various enterprise, and diffuse and evaporation causes the formation of the steam of these salt, the steam of these salt will be deposited on analyzing container window.
The task of proposed invention improves the consumptive characteristics of watch-dog, increases the unattended time of described watch-dog and guarantee the long-term operation of described watch-dog.
Set task is realized by a kind of mercury watch-dog, described mercury watch-dog comprise input sample unit, Thermospray, can by analyzing container, gas collector unit and the sucking-off pump heated, described analyzing container comprises two windows, at least one input gas ports and at least two output gas ports, described two windows are transparent and for the resoance radiation of mercury, described analyzing container (at least) is via a window in described two windows and Atomic Absorption Spectrometer optical coupled; At least one input gas ports described is arranged in the middle body of described analyzing container, and described at least two to export in gas ports each all in input gas ports with accordingly between window, wherein said sample input block connects with syringe pump, analyzed sample can be incorporated in described Thermospray by described syringe pump, and described analyzing container has the opening be positioned in its two ends, described opening is between described window and nearest described output gas ports, and gas can be supplied to via described opening.
Essence of the present invention is, shielding gas flow results between the described window of analyzing container and analyzed gas, prevents the analyzed gas arriving the heat in described analyzing container from directly contacting with the cold surface of described window.Because this is true, the high volatility compound steam be present in described analyzed gas can not condense on the described window of described analyzing container, and the transmission coefficient of the probe radiation for described atomic absorption analyzer of described window remains on the lasting a very long time in working range.
Described mercury watch-dog also comprises sprayer and retainer thereof, cavity is produced between the inwall and described sprayer itself of described retainer, described cavity is connected with the internal cavities of described Thermospray, and described retainer itself comprises the port be connected with vector gas supply part by produced described cavity.Described sprayer comprises nozzle, fluid inlet port and gas entry ports, and described gas entry ports is by means of gas liquid connectedness and described vector gas supply part.Described vector gas supply part comprises the mixer with three ports; In described three ports, the first port is connected to carrier gas body source, and the second port is connected to water supply part, and the 3rd port is connected to described second port of described sprayer.
In addition, described gas collector unit is connected by the output port of gas liquid connectedness with described analyzing container, and comprises gas liquid separation vessel and liquid collection reservoir.
Finally, described analyzing container is connected via first window with described spectrometer optics and is connected with retroreflector via Second Window, the mode that described retroreflector is assigned with is, the probe radiation of having led to described Second Window via described first window of described spectrometer should return via described Second Window and turn back to described spectrometer via described first window.
In mercury watch-dog required for protection, use described sprayer to allow for described atomizer eliminate mechanical type water sample supply part; the reliability of this device that allows to increase supply; and the sample of input aerosol form, this gasoloid decreases the amount of the salt be deposited on atomization wall.Water is supplied in sprayer compressed air hose the amount allowing to reduce the salt of Direct precipitation in its nozzle.Described gas liquid separation vessel is installed after described analyzing container allow to remove water vapour from output gas flow, thus eliminates the condensation of water in sucking-off pump and provide normal operator scheme for it.Make the radiation through described analyzing container enter in retroreflector, turn back to then lead in described analyzing container photodetector optical plan allow in the identical linear dimension of analyzing container, the sensitivity of analysis is doubled.In addition, such scheme provides compact spectrometer architecture, which increases the job stability of whole spectrometer.
The essence of claimed invention is illustrated by figure below:
Fig. 1 is the process flow diagram of mercury watch-dog.
Fig. 2 is the process flow diagram of the input block with sprayer and gas supply member.
Fig. 3 is the process flow diagram of gas collector unit.
Fig. 4 is the protection scheme of analyzing container window.
Fig. 5 is the figure that the sensitivity of the flow of sucking-off pump relies on.
Fig. 6 is the photo of the aerocolloidal model of water spray in Thermospray.
Fig. 7 is the photo of analyzing container window, and wherein A is the photo operated when having shielding gas flow after 14 days, and В is the photo operated when not having shielding gas flow within 8 hours.
The mercury watch-dog that its process flow diagram presents in FIG comprises: infusion pump units 1, sample input block 2, Thermospray 3, have window 5 and have input gas ports 6 and export the analyzing container 4 of gas ports 7, gas collector unit 8, sucking-off pump 9 (being hereinafter referred to as reflux pump) and Atomic Absorption Spectrometer 10.The case of analyzing container has opening 11 between window and output port.
Infusion pump units 1 can perform as follows (Fig. 2).Sprayer 13 is arranged in sprayer retainer 12 by the mode being guided to the interior section of Thermospray 3 such to make its nozzle, and all assemblies are all installed in sample input block 2.The fluid port of sprayer 14 is connected to switching fluid tap (not illustrating in the drawings), and the designated port of sprayer is alternatively connected with distilled water reservoir, standard solution and sample to be analyzed by switching fluid tap.The gas ports of sprayer 15 is connected to the first port 16 of mixer 17, and the second port one 8 of mixer 17 is connected to water supply part 19, and the 3rd port 20 of mixer 17 is connected to vector gas supply part 21.Vector gas is also fed into the cavity between sprayer and sprayer retainer via retainer port 22.
When determining the mercury content in burning gases, infusion pump units 1 can make the form of membrane pump, and analyzed gas is directly supplied to Thermospray 3 from sample line (not illustrating in the drawings) by membrane pump.
Thermospray 3 can perform as quartz ampoule, and its one end is attached to sample input block 2 hermetically, and the second end is attached to the input port 6 of analyzing container 4 hermetically.Quartz ampoule be installed into sprayer 13 and retainer 12 coaxial, and the internal diameter of quartz ampoule is not less than the internal diameter of sprayer retainer 12.Temperature inside the quartz ampoule well heater maintained within the scope of 600-700 DEG C is installed in the outside of quartz ampoule.Whole Thermospray is placed in metal coating shell.
Analyzing container 4 can make the form of cylinder, makes input port 6 be welded to center section hermetically, and two band frame windows 5 are installed on its butt end.Output port 7 is installed between window 5 and input port 6 in those both sides close to window.In order to form shielding gas flow, opening 11 is arranged between window 5 and output port 7, or air can be installed between window 5 and output port 7 through its extra input port entering analyzing container.The well heater that the temperature of analyzed gas maintains within the scope of 600-750 DEG C is installed in the interior section of analyzing container.
Gas collector unit 8 can carry out following (Fig. 3).The output port 7 of analyzing container 4 is connected to gas liquid separation vessel 24 by superheated vapor connectedness 23, gas liquid separation vessel 24 can make the form of backflow refrigerator, water flowing in the external condensation device cover of this backflow refrigerator of cooling, and superheated vapor potpourri enters its interior section.One end of separation vessel 24 is connected to liquid collection reservoir 25, and after the cooling of superheated vapor potpourri, water enters liquid collection reservoir 25.Second end of separation vessel 24 is connected to the sucking-off pump 9 performed as membrane pump.
Atomic Absorption Spectrometer 10 can make the mercury atom absorption analysis instrument [4] with direct Zeeman effect, it is characterized in that high measurement selectivity.
Let us considers the mercury monitor operations determining the example of the total content of mercury in the fresh water (FW) of cogeneration plant.Details as the fresh water (FW) of evaluating objects is, it comprises by the high concentration kieserohalosylvite (1 – 5%) dissolved.Water to be analyzed enters the tank of the input being connected to switching fluid tap.Other input of valve is connected to distilled water reservoir, and standard solution is necessary blank measure and the calibration of carrying out watch-dog.
The output of switching fluid tap is connected to the fluid port of sprayer.Compressed air source is connected to the gas ports of sprayer.Such as to be produced in the region of gas nozzle by the pressurized air of dust and greasy dirt steam purifying by pass through the dust of sprayer and greasy dirt filtrator and vacuumize (venturi-effect), this causes the fluid passage pumping liquid from sprayer and makes liquid enter gas nozzle.In gas nozzle, achieve the liquid slowly introduced by fast air stream, this causes the formation of water aerosol, makes water aerosol enter Thermospray further.
In the Thermospray that temperature is within the scope of 600 – 700 DEG C, water evaporates from aerosol particle, and all mercury be included in aerosol particle convert atomic form at such a temperature.When water evaporates, the salt (salt gasoloid) of little solid particle is formed and is present in the suspending liquid of vector gas.The component of other all formation is transported in the unit of analyzing container via its input port by vector gas.
Meanwhile, air enters analyzing container via the opening in window, prevents analyzed gas from contacting with the direct of window surface.Superheated vapor potpourri enters from the output port of analyzing container the gas liquid separation vessel making backflow refrigerator via gas three-way pipe, the water of cooling flows in the external cooling jacket of gas liquid separation vessel.
Second end pipeline of gas three-way pipe is connected to liquid collection reservoir, and the water condensed in backflow refrigerator is collected in liquid collection reservoir.Pipeline is installed so that its second end in liquid collection reservoir is positioned at (when watch-dog starts, the extra water yield is filled in this reservoir) such mode below water level always, thus the lock water function of the gas fraction carried into execution a plan.Second end of backflow refrigerator is connected to reflux pump, induces sucking-off air-flow after analyzing container.
When water aerosol is formed in inside sprayer, the aerocolloidal partly precipitated formed is on the inwall of gas nozzle.Because analyzed water comprises the kieserohalosylvite of high concentration, water causes salt accumulation on the inside surface of gas nozzle from precipitated aerocolloidal evaporation, and this causes the quick pollution of the change of nozzle geometry and sprayer.In order to eliminate the pollution of sprayer, the distilled water of additional quantity is introduced in compressed-air actuated pipe, and washes out nozzle continuously and therefrom remove precipitated salt.
When water aerosol is expelled in Thermospray (Fig. 6), aerocolloidal this part directly evaporate in vector gas, and this part (water does not evaporate completely) successfully arrives the heated wall (being placed on the quartz ampoule 26 in well heater 27) of atomizer, and it is determined by 28 water aerosol 29 spraying limited angle.In order to increase the time exhausted by the water aerosol in vector gas, air stream 30 is injected between sprayer and sprayer retainer in addition.
In addition, this extra air stream extends along the wall of Thermospray, thus remains in the axial region of atomizer by aerocolloidal main flow, wherein in fact the evaporation of water from aerosol particle and the generation of salt gasoloid 31 occurs.The increase of water aerosol 32 movement locus causes the share of water aerosol in vector gas by evaporating to increase, and causes the rate of deposition of salt 33 on the wall of Thermospray to reduce, thus causes the operation life of unmanned Thermospray to increase.
Transport in the aerocolloidal process of salt inside atomizer and by the analyzing container (analyzing container temperature is 650 – 750 DEG C) that heats, salt compound evaporates from aerosol particle surface portion, and passes into vector gas as a vapor.Similarly, the salt compound be deposited in when heated on atomizer surface partly evaporates and passes into vector gas.Finally, when the surface interaction of the well heater of salt particle and analyzing container, the evaporation of heating coil material component ground, and its steam passes into vector gas.
In order to eliminate the sedimentation effect of steam from the vector gas analyzing container window surface of high volatility compound, analyzing container is designed to have the window with the blowing that purifies air, and vector gas is not directly contacted with analyzing container window.Present the protection scheme of analyzing container window in the diagram.Gas is pumped out from analyzing container via output port 7, space velocity V1=V11+V12.Analyzed gas is supplied via input port 6 with space velocity V2.Reflux pump 9 produces respectively and vacuumizes in output port and analyzing container, and analyzing container pressure is lower than atmospheric pressure.Due to vacuumizing in analyzing container, create the stream of ambient air in analyzing container.Because opening next-door neighbour output port, so the air produced flows to into opening and leaves at once via output port, and not along the Axis Extension of analyzing container.
The speed V1 of reflux pump is higher than the feed speed V2 of the gas analyzed in analyzing container, and therefore, shielding gas flow speed V3=V31+V32 will make value V3=V1-V2.Measurement sensistivity is given when the constant feed speed V2=2 liter/min of analyzed gas to the dependence of reflux pump speed V1 in Fig. 5.If pumping rate is lower than feed speed (0-2 liter/min), then analyzed gas occupies whole analyzing container, comprise the region between output port and analyzing container window, sensitivity is maximum (under existing experiment condition, the effective length of sensitivity and analyzed gas blanket is proportional).
When increasing pumping rate (2-4 liter/min), the analyzed gas from the region between window and output port is replaced by air, and correspondingly, measurement sensistivity reduces.Further increase pumping rate (4-9 liter/min) can cause the inappreciable change of sensitivity, that is, increase pumping rate only causes and increase shielding gas flow in the insignificant situation of the reduction of the effective length of analyzed gas blanket.
The result that the aerial concentration of mercury will make the air entering analyzing container (together with mercury) should not affect mercury measurement in water sample.In our case, the concentration of mercury should more than 6 μ g/m
3value (under the level of 10% 1 hour stability), this value is no better than working area (10 μ g/m
3) in threshold value can safe level.The modified node method of analyzing container unit is tested by the real water sample of analysis.Fig. 7 shows picture A and the B of the window having shielding gas flow and do not have shielding gas flow.Given figure allows to conclude: the window with protection stream keeps running (probe radiation of Atomic Absorption Spectrometer is through the middle body of window) after 14 days, and does not protect the window of stream to enter non-operating state in operation after 8 hours.
Other Working Examples of mercury watch-dog is the mercury content determined in burning gases.Burning gases have quite complicated composition: smoke particle, water vapour, O
2, CO
2, NO, NO
2, SO
2, HCl, HF, Hg and compound etc. thereof.In addition, the temperature of sampling spot gas is 100 – 200 DEG C.Sampling probe is connected with pumping unit (syringe pump heated with gas line).As syringe pump, we advise using have all elements all with the membrane pump of the polytetrafluorethylecoatings coatings of air flow contacts.
The output of forcing pump is connected to sample input block, and after this analyzed gas enters Thermospray, and the temperature of Thermospray is 800 – 950 DEG C.
This temperature is enough to fixing mercury to be converted to element form, and is enough to the oxygenation efficiency considerably reducing mercury element.Gas from Thermospray is transported in the analyzing container being heated to 850 – 950 DEG C via the input gas ports of analyzing container.In order to protecting window prevents the precipitation of the volatile compound be present in analyzed gas, analyzing container has the structure that its window external purification air is dried, and this prevents window from contacting with the direct of analyzed gas.The output gas ports of analyzing container is connected to gas collector unit, and wherein the temperature of analyzed gas is reduced to the level that tolerable performs the sucking-off pump work for membrane pump.Along with reflux pump is higher than the flowing of forcing pump, this causes difference to flow through the outward appearance of the opening in the region of analyzing container window, and protecting window is from pollution.
Thus the present invention allows operatorless for the mercury watch-dog time interval to increase at least 40 times.
Reference
1、http://www.mercury-instruments.de/EN/products/downloads/Mercury-Instruments-PA-2-en.pdf
2, the 5th, 679, No. 957 United States Patent (USP)s
3, http://www.sick.com MERCEM300Z mercury analyzer
4, А. А .Ganeev, S. Е .Shopulov, M.N.Slyadnev " Zeeman modulationpolarization spectrometry as variance of atomic – absorption analysis:possibilities andconstraints ", JAC, 51 volume 8 phase 855-864 pages in 1996
Claims (6)
1. a mercury watch-dog, described mercury watch-dog comprise input sample unit, Thermospray, can by analyzing container, gas collector unit and the sucking-off pump heated, described analyzing container comprises two windows, at least one input gas ports and at least two output gas ports, described two windows are transparent and for the resoance radiation of mercury, described analyzing container is at least via a window in described two windows and Atomic Absorption Spectrometer optical coupled, at least one input gas ports described is arranged in the middle body of described analyzing container, and described at least two export in gas ports each all input between gas ports and corresponding described window, wherein said sample input block connects with syringe pump, analyzed sample can be incorporated in described Thermospray by described syringe pump, and described analyzing container has the opening be positioned in its two ends, described opening is between described window and nearest described output gas ports, gas can be supplied to via described opening.
2. mercury watch-dog according to claim 1, wherein, described syringe pump comprises sprayer, and described sprayer has nozzle, fluid inlet port and gas entry ports, and described gas entry ports is connected with vector gas supply part by means of gas liquid connectedness.
3. mercury watch-dog according to claim 2, wherein, vector gas supply part comprises the mixer with three ports, in described three ports, first port is connected to carrier gas body source, second port is connected to water supply part, and the 3rd port is connected to described second port of described sprayer.
4. mercury watch-dog according to claim 1, wherein, described sample input block comprises the retainer of sprayer, cavity is produced between the inwall and described sprayer of the retainer of described sprayer, this cavity is connected with the internal cavities of described Thermospray, and the retainer of described sprayer comprises the port produced described cavity being connected to vector gas supply part.
5. mercury watch-dog according to claim 1, wherein, described gas collector unit is connected with the described output gas ports of described analyzing container by gas liquid connectedness, and described gas collector unit comprises gas liquid separation vessel and liquid collection reservoir.
6. mercury watch-dog according to claim 1, wherein, described analyzing container is via first window and described Atomic Absorption Spectrometer optical coupled, and described analyzing container is via Second Window and retroreflector optical coupled, described retroreflector is allocated such that, the leading to probe radiation in described Second Window via described first window and to return via described Second Window and to turn back in described Atomic Absorption Spectrometer via described first window of described Atomic Absorption Spectrometer.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| RU2013107775/28A RU2521719C1 (en) | 2013-02-15 | 2013-02-15 | Mercury monitor |
| RU2013107775 | 2013-02-15 | ||
| PCT/RU2014/000031 WO2014126507A1 (en) | 2013-02-15 | 2014-01-20 | Mercury monitor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN105008897A true CN105008897A (en) | 2015-10-28 |
| CN105008897B CN105008897B (en) | 2017-11-14 |
Family
ID=51217056
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201480008675.9A Active CN105008897B (en) | 2013-02-15 | 2014-01-20 | Mercury monitor |
Country Status (8)
| Country | Link |
|---|---|
| US (1) | US9389168B2 (en) |
| EP (1) | EP2957891B1 (en) |
| CN (1) | CN105008897B (en) |
| CA (1) | CA2901103C (en) |
| EA (1) | EA028028B1 (en) |
| RU (1) | RU2521719C1 (en) |
| UA (1) | UA113115C2 (en) |
| WO (1) | WO2014126507A1 (en) |
Families Citing this family (12)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10029290B2 (en) | 2013-11-04 | 2018-07-24 | Loci Controls, Inc. | Devices and techniques relating to landfill gas extraction |
| US10576514B2 (en) | 2013-11-04 | 2020-03-03 | Loci Controls, Inc. | Devices and techniques relating to landfill gas extraction |
| US10365214B2 (en) * | 2014-01-14 | 2019-07-30 | The Regents Of The University Of California | Method and device for detection and spatial mapping of mercury concentration in water samples |
| US10705063B2 (en) * | 2016-03-01 | 2020-07-07 | Loci Controls, Inc. | Designs for enhanced reliability and calibration of landfill gas measurement and control devices |
| WO2017151766A1 (en) | 2016-03-01 | 2017-09-08 | Loci Controls, Inc. | Designs for enhanced reliability and calibration of landfill gas measurement and control devices |
| CN107144671B (en) * | 2017-06-23 | 2022-04-19 | 中国电建集团贵阳勘测设计研究院有限公司 | Shale gas-water lock effect evaluation device and method under high pressure condition |
| WO2019173132A1 (en) | 2018-03-06 | 2019-09-12 | Loci Controls, Inc. | Landfill gas extraction control system |
| WO2020072457A1 (en) | 2018-10-01 | 2020-04-09 | Loci Controls, Inc. | Landfill gas extraction systems and methods |
| CA3168631A1 (en) | 2020-01-29 | 2021-08-05 | Loci Controls, Inc. | Automated compliance measurement and control for landfill gas extraction systems |
| US12090532B2 (en) * | 2020-07-13 | 2024-09-17 | Loci Controls, Inc. | Devices and techniques relating to landfill gas extraction |
| US11623256B2 (en) | 2020-07-13 | 2023-04-11 | Loci Controls, Inc. | Devices and techniques relating to landfill gas extraction |
| US11865594B2 (en) | 2020-12-03 | 2024-01-09 | Loci Controls, Inc. | Greenhouse gas emissions control |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679957A (en) * | 1996-01-04 | 1997-10-21 | Ada Technologies, Inc. | Method and apparatus for monitoring mercury emissions |
| CN1271858A (en) * | 1999-03-06 | 2000-11-01 | 痕量分析公司 | Photometric detection system and method for gas |
| US6344151B1 (en) * | 1997-12-31 | 2002-02-05 | Lam Research Corporation | Gas purge protection of sensors and windows in a gas phase processing reactor |
| EP1469299A1 (en) * | 2003-04-16 | 2004-10-20 | ABB PATENT GmbH | Measuring cuvette for a photometer, and method of use |
| CN1704180A (en) * | 2004-05-31 | 2005-12-07 | 三菱重工业株式会社 | Optical performance restoring equipment, restoring method and optical system used for the equipment |
| CN101681802A (en) * | 2007-03-21 | 2010-03-24 | 真实仪器公司 | Method and apparatus for reducing the effects of window clouding on a viewport window in a reactive environment |
| JP2011127988A (en) * | 2009-12-17 | 2011-06-30 | Mitsubishi Heavy Ind Ltd | Gas measurement cell and gas concentration measurement apparatus using the same |
| US20120161022A1 (en) * | 2009-03-11 | 2012-06-28 | Thomson Murray J | Apparatus for continuous in situ monitoring of elemental mercury vapour, and method of using same |
| CN102564986A (en) * | 2011-12-30 | 2012-07-11 | 北京雪迪龙科技股份有限公司 | Smoke mercury emission monitoring system and method |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| RU2110060C1 (en) * | 1995-10-03 | 1998-04-27 | Ганеев Александр Ахатович | Method of determining mercury if organic media |
| FR2742863B1 (en) * | 1995-12-22 | 1998-03-06 | Instruments Sa | DEVICE AND METHOD FOR INTRODUCING A SAMPLE FOR ANALYTICAL ATOMIC SPECTROMETRY FOR THE CONCOMITANT MERCURY ANALYSIS |
| RU2145082C1 (en) * | 1998-03-23 | 2000-01-27 | Общество с ограниченной ответственностью "ВИНТЕЛ" | Method determining elements in solutions and device for its realization |
| DE10011171A1 (en) * | 2000-03-08 | 2001-09-13 | Perkin Elmer Bodenseewerk Zwei | Process for detecting mercury in a sample solution comprises a detection device consisting of an atomic spectrometer with a measuring cell, a precious metal enriching device and a control unit for controlling the feed of gaseous mercury |
| US7454952B2 (en) * | 2005-05-02 | 2008-11-25 | Thermo Fisher Scientific Inc. | Method and apparatus for monitoring mercury in a gas sample |
| RU2010117689A (en) * | 2010-05-04 | 2011-11-10 | Александр Михайлович Аниканов (RU) | ATOMIC-ABSORPTION ANALYZER OF MERCURY |
-
2013
- 2013-02-15 RU RU2013107775/28A patent/RU2521719C1/en active IP Right Revival
-
2014
- 2014-01-20 CA CA2901103A patent/CA2901103C/en active Active
- 2014-01-20 WO PCT/RU2014/000031 patent/WO2014126507A1/en active Application Filing
- 2014-01-20 US US14/768,142 patent/US9389168B2/en active Active
- 2014-01-20 EP EP14751714.8A patent/EP2957891B1/en active Active
- 2014-01-20 CN CN201480008675.9A patent/CN105008897B/en active Active
- 2014-01-20 UA UAA201507348A patent/UA113115C2/en unknown
- 2014-01-20 EA EA201500771A patent/EA028028B1/en not_active IP Right Cessation
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5679957A (en) * | 1996-01-04 | 1997-10-21 | Ada Technologies, Inc. | Method and apparatus for monitoring mercury emissions |
| US6344151B1 (en) * | 1997-12-31 | 2002-02-05 | Lam Research Corporation | Gas purge protection of sensors and windows in a gas phase processing reactor |
| CN1271858A (en) * | 1999-03-06 | 2000-11-01 | 痕量分析公司 | Photometric detection system and method for gas |
| EP1469299A1 (en) * | 2003-04-16 | 2004-10-20 | ABB PATENT GmbH | Measuring cuvette for a photometer, and method of use |
| CN1704180A (en) * | 2004-05-31 | 2005-12-07 | 三菱重工业株式会社 | Optical performance restoring equipment, restoring method and optical system used for the equipment |
| CN101681802A (en) * | 2007-03-21 | 2010-03-24 | 真实仪器公司 | Method and apparatus for reducing the effects of window clouding on a viewport window in a reactive environment |
| US20120161022A1 (en) * | 2009-03-11 | 2012-06-28 | Thomson Murray J | Apparatus for continuous in situ monitoring of elemental mercury vapour, and method of using same |
| JP2011127988A (en) * | 2009-12-17 | 2011-06-30 | Mitsubishi Heavy Ind Ltd | Gas measurement cell and gas concentration measurement apparatus using the same |
| CN102564986A (en) * | 2011-12-30 | 2012-07-11 | 北京雪迪龙科技股份有限公司 | Smoke mercury emission monitoring system and method |
Also Published As
| Publication number | Publication date |
|---|---|
| EA028028B1 (en) | 2017-09-29 |
| EP2957891B1 (en) | 2018-03-07 |
| US9389168B2 (en) | 2016-07-12 |
| CN105008897B (en) | 2017-11-14 |
| EA201500771A1 (en) | 2016-01-29 |
| EP2957891A1 (en) | 2015-12-23 |
| RU2521719C1 (en) | 2014-07-10 |
| UA113115C2 (en) | 2016-12-12 |
| CA2901103C (en) | 2021-03-02 |
| EP2957891A4 (en) | 2016-11-16 |
| US20160033391A1 (en) | 2016-02-04 |
| WO2014126507A1 (en) | 2014-08-21 |
| CA2901103A1 (en) | 2014-08-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN105008897A (en) | Mercury monitor | |
| Hoffmann et al. | Atmospheric analytical chemistry | |
| Shilling et al. | Particle mass yield in secondary organic aerosol formed by the dark ozonolysis of α-pinene | |
| Trebs et al. | Real-time measurements of ammonia, acidic trace gases and water-soluble inorganic aerosol species at a rural site in the Amazon Basin | |
| Ali et al. | Denuder tubes for sampling of gaseous species. A review | |
| Cocker et al. | State-of-the-art chamber facility for studying atmospheric aerosol chemistry | |
| Hecobian et al. | Water-Soluble Organic Aerosol material and the light-absorption characteristics of aqueous extracts measured over the Southeastern United States | |
| Sullivan et al. | Recent advances in our understanding of atmospheric chemistry and climate made possible by on-line aerosol analysis instrumentation | |
| Pécheyran et al. | Simultaneous determination of volatile metal (Pb, Hg, Sn, In, Ga) and nonmetal species (Se, P, As) in different atmospheres by cryofocusing and detection by ICPMS | |
| Weber et al. | A particle-into-liquid collector for rapid measurement of aerosol bulk chemical composition | |
| Edney et al. | Impact of aerosol liquid water on secondary organic aerosol yields of irradiated toluene/propylene/NOx/(NH4) 2SO4/air mixtures | |
| Xu et al. | Aerosol liquid water promotes the formation of water-soluble organic nitrogen in submicrometer aerosols in a suburban forest | |
| Sipin et al. | Recent advances and some remaining challenges in analytical chemistry of the atmosphere | |
| Baxter et al. | Determination of mercury by atomic absorption spectrometry using a platinum-lined graphite furnace for in situ preconcentration | |
| CN109342284A (en) | A kind of detection system and detection method for harmful substances from flue gases | |
| McClenny et al. | Preparing to measure the effects of the NOX SIP Call—methods for ambient air monitoring of NO, NO2, NOY, and individual NOZ species | |
| Vogel et al. | Aerosol chemistry resolved by mass spectrometry: Linking field measurements of cloud condensation nuclei activity to organic aerosol composition | |
| Li et al. | Detecting pH of sub-micrometer aerosol particles using fluorescent probes | |
| US9110048B2 (en) | Devices and methods for measuring the acidity of airborne matter using UV-visible spectrometry | |
| Olszyna et al. | Effect of ambient NH3 levels on PM2. 5 composition in the Great Smoky Mountains National Park | |
| CN105044049A (en) | Method and device for measuring volatile compounds | |
| Kiendler-Scharr et al. | Introduction to Atmospheric Simulation Chambers and Their Applications | |
| Alexa et al. | Simultaneous determination of gaseous ammonia and particulate ammonium in ambient air using a cylindrical wet effluent diffusion denuder and a continuous aerosol sampler | |
| Hirokawa et al. | In situ measurements of atmospheric nitrous acid by chemical ionization mass spectrometry using chloride ion transfer reactions | |
| Yanaga et al. | Formaldehyde vapor produced from hexamethylenetetramine and pesticide: simultaneous monitoring of formaldehyde and ozone in chamber experiments by flow-based hybrid micro-gas analyzer |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| TA01 | Transfer of patent application right |
Effective date of registration: 20171024 Address after: Hongkong Chinese Chai Applicant after: Hongkong Lumei cosmos Holdings Limited Instrument Address before: Russia St Petersburg Applicant before: Stroganov Alexander Anatolyevich Applicant before: S*E*Holuperv Applicant before: P*V*Pidimurov |
|
| TA01 | Transfer of patent application right | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |